Hydrogenated or hardened oil and process of making same.



G. ELLIS.

HYDROGENATED 0R HARDENED OIL AND PROCESS OF MAKING SAME.

APPLICATION FILED NOV. 22, 1912.

1,097,308. I PatentedMayl9,191L

7 V lnve or:

UNITED sTATEs PATENT OFFICE.

CARLETON ELLIS, OF MONTCLAIR, NEW JERSEY.

HYDROGENATED Ol't HARDENED OIL AND PROCESS OI MAKING- SAME.

i ,oo7,sos.

- Specification of Letters Patent.

Patented May 19, 1914.

Application filed November 22, 1912. Serial No. 732,943.

To all whom it may concern:

Be it known that I, CARLETON ELnIs, a citizen of the United States, and a resident of Montclair, inthe county of Essex and State of New Jersey,- have invented certain new and useful Improvements in Hydrogenated or Hardened Oil and Processes of Making Same, of which the following is a specification.

This invention relates to edible fats and the like, comprising oil or fat, such as by drogenated oil, hardened by catalytic actionand particularly to mixtures of such fats or oils with other oils; all essentiallyor substantially free from toxic bodies including freedom from harmful or undesirable re,- sidual traces of catalytic bodies such as nickel or copper: all as more fully hereinafter described.

Some oils proposed or intended for edible purposes contain nitrogenous or other bodies of a deleterious or'toxic character which may be destroyed by oertaintreatment as by certain conditions of hydrogenation without charging with metal poisons so that the oil or fat becomes safely edible and without cumulative and dangerous efiects when taken in large quantities for protracted periods. For a high rade edible product a composition'essential y or substantially free from the foregoing objectionable bodies is desired. Among the vegetable oils corn, cottonseed,

soy bean, peanut, sesame, olive, rape, co-

coanut, caster and palm oils or animal oils such as those of lard and tallow and other olelns. and palmitins with more or less stearins, of an animal'nature, fish and whale oils, codlivcr oil and the like may be employed" either in the hydrogenated or unhydrogenated condition in compounding products under the present invention.

palmitate, stearate'etc.

In the hydrogenation of oils with the aid of, nickel and copper catalyzer, compounds and the like considerable dlfliculty exists because of the solution of some of thecata:

lyzerby the oil. Although a substantially neutral oil be taken for hydrogenation, during the operation a certain small amount of fatty acid is liable to-be set free, and at the.

temperatures employed the catalyzer passes more or less into solution as an oleate, Thus the oil carries a body of toxic nature which may be present in an amount to exert a. banefufll effect as a cumulative or progressive poison. Under the present invention I may, for example,

associate-a catalyzer of this character with a nullifying agent, the purposeof which is to render the catalyzer metal resistant to the solvent action of free fatty acids. By this means a new product is secured namely, a catalytically-hydrogenated edible fat essentially or substantially free from toxic traces of n1ckel or othensimilar catalyzer-metal compounds. j One manner of carrying out the present nvention is to prepare a catalyzer by admixing a concentrated solution of nickel niing agents such asthe oxids, hydrates, car-- bonates, etc., of calcium and magnesium likewise may be used. Thus there is obtained an edible oil product comprising an edible catalytically-hydrogenated fat entirely devoid of traces of nickel or of nickel in essentially toxic amounts.

Nickel in the metallic form generally speaking is not as soluble in glycerids as nickel oxid. If by the action of steam due to reductionof the carbonyl group or otherwise, the glycerid is hydrolized the .fatty acids attack nickel oXid, but do not tend as readily to dissolve metallic nickel owing to the mass action ofthe hydrogen gas. Dry hydrogen preferably should be employed in treating the oil even under these conditions, but the gas should not be under excessive pressures. It is somewhat easier to harden certain oils by using a high pressure of hydrogen, but this may be compensated for by employing a highly responsive catalyzer.

Regenerated nickel catalytic material may be used to advantage in edible fat manufacture. To thisend the spent'catalyzer may be washed with naphtha to remove most of I the adhering fat and to further purifyiit maybe heated in an atmosphere of oxygen or ozonized oxygen until free from benzol insoluble'organic compounds and then ,re-

effectively without running up the temperature to a lpoint where high sensitivity is lost. Furt er, in reference to makin catalyzer for the purposes aforesaid, it s 'ould be stated h t nickel sulfate may be used instead ofnickel nitrate mentioned above. If nickel sulfate is -mixed with slaked lime nickel, hydrate and calcium sulfate are produced. This mixture may be dried and ignited in hydrogen. The dried material. is

- fal-11ng tionary which is that point where solidificaignited in a current of hydrogen or other suitable reducing g'as when it use as a catal zer. Similarly, other nickel salts such asmckel fluosilicate maybe mixed with lime or other base to effect the required metathesis. Ordinarily, however, I prefer to. secure a product of a consistency .expressed as the solidifying point of said product of a range approximately from above 15 C. to below 35 C. It,of'cou'rse, may vary within still greater limitsf 'according' to climate and seasonal variationsxofatmosheric temperature. In general ai product having a titer of from 25 7 wellsuited as land substitute olf-lard compound. 'It should be noted thatthe term titer, as herein employed is that not rigidly 'recise thermometric value derived by coolm'g some of the melted product (not the fatty acids) and taking the point where the thermometric column becomes station'takes place. The titer of the fat is usually lower than the melting point.

For the manufacture of butter substitutes other conditions obtain. A softer roduct is desired, one in particular whic when taken into the mouth immediately melts and does notleavea disagreeable greasy sensation on the tongue and walls of the month. In themanufacture of h drog'enated butter substitute as I have set orth in U. S. Letters Patent No. 1,038,545 of Sept. 17, 1912, the etc of over or'super-hydrogenation is desirab e. In the above mentioned patent I have specified in articular the manufacture of a butter su stitute involving the incor oration of h drogenated edible oil and mil material. t is also possible to make a butter-like composition without the use of milk material, but consisting of simply edible hydrogenated oil with perhaps some flavoring material as valerian ester and the like, salt and coloring matter. The mixture of edible hydrogenated vegetable oil with ordinary butter-in a proportion of two parts of the oil to onejpart of the butter provider-z verysuitable butter-like material at a rela- 1 s tively low'cost. Hydrogenated corn oil, be-

cause of its flavor is desirable for use in this "wa- While the procedure of making an edi legbutter or lard-likecompound varies is ready for C. to'-28 C. is-

cording to circumstances.

somewhat de ending upon the oils or fats treated and egrees of consistency desired, etc., for illustrative purposes, an edible mlX- ture is pre ared' by taking cottonseed oil and corn oi in the proportion of 4 parts of the former to one part of the latter. The almost tasteless character of cottonseed oil when hi hly refined and also when somewhathy rogenated is improved by the addition of corn or peanut. oil givin the product sometimes a faintl nutty avor. The mixture may be superiydrogenated by the action of hydrogen in the presence of a catalyzer to a titer of 35 to 40 C. .This is cooled and pressed to titer of say about 26 C. It is'agitated and heated with 5% more or less of fullers earth for about one hour and after filtration is ready for packaging. Or the pressed super-hydrogenated cottonseed oil product obtained in this way may be mixed with about 15% or 20% of corn oil to secure the titer desired.

Wherever the terms 011s and 'fat have been used herein they are applied as is common in this art 1n a sense which is's1ibstantially synonymous. l e

In the case of oils containing considerable quantities of fatty acids, I prefer to distil these with steam under reduced atmospheric pressure, to remove the deleterious acid material, leaving the fatty mixed esters in substantially pure condition and in a form readily susceptible to the action of hydroen. g By the present invelition cocoanut oil may be used and may be hydrogenated or not accocoanut oil alone or ordinary refined cocoanut oil mixed with hydrogenated cottonseed, corn or peanut oil and the like may be used as a fluxmg agent for chocolate in manufacture of confectionery. The melting point of the-fatty flux should preferably be about 90 F. to 100 F. Hydrogenated unpressed bring the product to av Hydrogenated ion cocoanut oil or hydrogenated cocoanut oil--- olein' or stearin may be used in a similar manner. 3 p

The manufacture of the coatin of chocolate creams calls for a relatively liigh melting .point fat which incorporates readily with chocolate and does not impair the flavor thereof. Cocoa butter is especially desired on this account, but is relatively expensive. Cocoanut oil melts so easily that in hot weather candies made with it melt very quickly when handled. Cocoanut oi hasalso a tendency to rancidify.

- In the manufacture of butter substitutes using cottonseed oil it is desirableto hydronafl until the iodin number falls to' 80 or therea'bout. The oil may thenbe cooled to about 309. G. or so, and allowed to stand for a time and pressed to remove the excess of stearin. It is'then melted or warmed to render it entirely fluid, and is incorporated with milk material. Suitable material of this character is ordinary full milk or skim milk or buttermilk, StBIlllZKlllllk, sour milk which has been specially afiermented using lactic acid fermentand the lik Salt to the extent of 2% to 8% or thereabout, may be added according to the degree of saltiness desired. Suitable coloring material such as ordinary butter color, and also flavoring compounds, may be likewise added. Of the oils mentioned cottonseed and peanut oil are especially suitable, while corn and soy bean oil also are adapted foruse in this way. Various other oils may also be incorporated if desired, such as lard and tallow oil, almond oil, olive oil, rape seed oil, cocoanutoil and the like may be added in various proportions, although in general it should be stated that; the product essentially or preferably should consist of vegetable oil. If oils other than those set forth as preferable in the, present inventionare employed, it is desirable also to hydro-. genate these to improvetheir odor.- Cocoanut oil here is not generally speaking desirable, because of the fact that it has a tend-- ency to become rancid in the presence of ture.

moisture. The flavor of cocoanut oil is, however, desirable and this may'be used more or less, particularly if somewhat hydrogenated, or if substantially free of moisture. With less'than 5% moisture a refined oil remains neutral for some time.

A dry butter substitute of about the melting point of butter may be made by compounding 12 parts soft hydrogenated cottonseed oil; 3 parts of refined cocoanut oil and 31} parts of good palm oil. Or, 6 parts hydrogenated cottonseed oil and '6 parts or more of cocoanut oil may be mixed and heated to 212 F. or so to remove mois- Palm oil whenfreed from undesirable ex cess of free fatty acids and then.hydro-' gen-ated, forms a desirable blending fat for butter substitutes. It mixes with hydrogenated cottonseed oil without seeding? on standing, that is, does not granulate and separate in an undesirable way. While raw palm oil is. rather-unpalatable, I the refined hydrogenated product is adapted for use as an edible oil. A palm oil butter substitute containing milk material may be prepared by substituting this oil,-refined and prefer ably hydrogenated, in the above milk-containing-formulas. i

A substantially dry butter substitute may be made -from-hydrogenated cottonseed oil 15 parts; palm oil 4 parts and butter fat "'1' partywith which maybe'incofporated salt and special fiavorin agents.

Hydrogenated fis or whale o1l similarly maybe used as a basis of mpisture-cont'aim ing or'dry butter substitutesfand other ediwhat more easily with neutral oils than with those containing large amounts of free fatty acids and there is less likelihood that. metal will be dissolved from-the catalyzer by the oil when the latter is neutral.

Purification ofthe oil in the manner described in.Seri'al No. 694,953 filed May 3, 1912, and-Serial No. 693,219 filed April 25, 1912, or otherwise may therefore, if desired, precede the step of hydrogenation. It should be stated, however, that with some fats at least stability is in part dependent on'the amount of handling the fat has experienced. Minimizingthe handling lends to stability in flavor in some cases. The treating receptacles in which hydrogenation is carried on preferably should be lined with enamel.

' The super-hydrogenation of fish oil converts the esters of the series of fatty acids O H O into comparatively odorless saturated compounds. .Glyceryl clupanodonate, a body largely responsible for the disagreeable odor of fishiloil, is converted into tity is not conducive to effective action of When present in any masome catalyzers. terial proportion the oil should be washed with an alkaline solution prior to hydrogenation.

" The accompanying diagrammatic drawings show, mainly in section, apparatus in nvention accordance with the present whereby the product of the invention may be prepared to good advantage.

In the drawings F 're 1 is a verticalsection of a receptacle fitted with inductors. Fig; 2. is a detail section of an inductor, while Figs. 3 and 4 are horizontal sections of. receptacles showing diiferent arrangements of inductor inlets. I

In Fig. 1, 1 is'a receptacle which is filled with oilto the level shown by the dotted line 2, 3 is a heating coil and 4 is a pump or circulatory means having suctionpipe 5 extendlng to nearly the bottom of the receptacle 1. The discharge outlet from thepump 4 is connectedwith pipe 6 to which is attached an inductor, of which thre'e are. shown in the'present illustration, these bejing'8, l1 and 13, cont-rolled by the valves igc ceptacle. In the latter case a pipe communicates with the upper part ofthe recep- I that shown by the type 8, or that shown by 11. or13. Hydrogen gas is supplied as retacle. 17 is an inlet for oil or catalyzer and 19 is a draw-off valve.

In Fig. 2 the inductor is shown in detail, 21 being the oil inlet; 22 a gas inlet; 23 a series of nozzles and 24 multiple stage induction efiect. 20 is a valve for testing inductive force, or for the admission of gas.

Fig. 3 shows three inductors arranged at angles of 120 from one another, the admission of the oil being radical.

Fig. 4 shows a substantially tangential admission of oil, two" members operating in opposition to a third member.

The operation of this apparatus is as follows: Oil is placed in the receptacle 1 and catalyzer is added, this catalyzer being preferablv finely-divided reduced nickel with a limeprotective agent or equivalent material and when the oil has reached the required temperature of say 150 to 160 C., more or less, the pump 4 is put into operation and oil mingled j with finely-divided catalyzer is drawn from the bottom of the receptacle and passed into the distributing pipe 6.

When the valve 9 is opened the oil passes from the inductor 8 and discharges above the level of the oil 2. The space above the oil is filled with. hydrogen gas or any suitable hydrogen-containing gas and by the inductive action of the jets produced by the nozzle 23-, gas is drawn into the inductor at 22 and mingles with the oil discharging above the level of the body of the oil 2.

' In. the case'ofthe inductor 11, the oil and gas discharge beneath the oil level and the gas bubbles In the case of the inductor 13, which by the way may be set at any suitable height with respect to the receptacle 1, hydrogen gas is lntroduced from the pipe 15 and the mixtureof oil and gas in a thoroughly commingled condition discharges into the body of the oil in the receptac e. a

. In Figs. 3 and4 the duplication of inductors such as are shown at 13 provides for a vvery satisfactory distribution of the gas through the oil. It should be stated that the apparatus may be operated by the means of a single inductor, such for example,'as

\ quired during the operation and the treated pil is withdrawn at 19.. Before doing this it v1s, however, desirable to allow the c'atalyzer to settle and draw off clearoil as far as possible. To this end'the draw-ofi '19 is set a suitable distance above the bottom of the tank in order to afiord-a deposition'pocket' tor the cataly'ter. It is not, of course, usuthrough the body of the oil.

ally possible to retainalllthe catalyzer in this manner, especially when it is in a very I finely-divided condition.

A fat com sition of lard-like consistency may be ma e by mixin hydrogenatedoil of a high titer and free rom toxic traces ofv catalyzer. with deodorized cottonseed oil. To this end I hydrogenate cottonseed oil to a fatty titer of say 52 and suitably mixwith refined deodorized cottonseed oil. A rela tively small proportion of the .52 titer fat sufiicesfor maklng the product aforesaid. The entire mixture may be deodorized by treating with super-heated steam at a temperature of about 400 F., and under a vacuum of about 28 to 29 inches of mercury.

To reca itulate, my invention relates to butter or ard substitutes or compounds or other edible fats and the like or roduct's intended for the preparation of edi le fats;

comprising such products essentially or substantially free from toxic bodies including catalyzer material of the nature of nickel or copper or similar active metals whose oxids' rather easily 1 dissolve in heated oil, especially when the latter contains fatty acids either originally present or formed during the hydrogenatlng process; which products may be obtained, for exampif by incorporating with the catalyzer a dy capable of restraining or preventing solution of the catalytic material in the oil or fat, by using and maintaining the catalyzer essentlally in by avoiding excessive gas pressures.

What I claim is: I

1. An edible oil product comprising edible composite fatty hydrogenated material essentially free from heavy metal toxic compounds.

- 2. An edible oil product comprising edible .a metallic state, by using dry hydrogen, and

composite fatty-hydrogenated material es sentially free from catalytic metal comounds.

3. An edible oil product comprising edible composite fatty hydrogenated material of at least butter-like consistency essentially free from heavy metal compounds.

4. An edible oil product comprising edible composite fatt hydrogenated material of substantially ard-like consistency essentially free from catalytic metal compounds.

v 5. An edible oil product comprising catalyticall -hardened edible cottonseed oil of substantially lard-like consistency free from dissob'ed metal catalyst.

6. The rocess of hydrogenatin terial to orni non-toxic edible fits which comprises treating said "material with hydrogen in the presence of an all-metal catalyzer and in maintaining said catalyzer in the metallic state during hydrogenation. .7. The rocess of hydrogenatin oily material to orm non-toxic edible ats which comprises treating said material -with oily ma-f hydrogen in the presence of an al1-nickel cataiyzer and in maintaining said catalyzer in the mstztllic stats during hyctrogenation.

8, The prosess of hy irogenatins eily matetistl ta tmm non-toxic edible iats which comp-rises treating said material with hydmgen in tha presence of a, metal catalyzer comprising nickel asseciztted with a fatty 3616i neutralizing agent and in main- 10 taining the active catalytic material in substantially a, metallic state during hydrogenation.

Signed at Montclair, in the county of Essex and State of New Jersey this 21st day of November, A. D. 1912. I

@ARLETON ELLIS. 

